CN104577043B - Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof - Google Patents
Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a manganese oxide/zinc oxide composite nanotube array thin film electrode material and a preparation method thereof, wherein the method comprises the following steps: (1) impregnating a substrate with anhydrous ethanol, soaking the substrate impregnated with the anhydrous ethanol in a solution of zinc nitrate and hexamethylenetetramine, and carrying out a first hydrothermal reaction, to generate a zinc oxide nanorod array thin film on the substrate; and (2) soaking the substrate obtained in the step (1) and generated with the zinc oxide nanorod array thin film in a manganese nitrate solution, and carrying out a second hydrothermal reaction. The preparation method has no need of a template removal step and a thin film further transfer process, and has the advantages of simple process and convenient operation. In addition, the manganese oxide/zinc oxide composite hollow tubular structure is used as a negative electrode material of lithium batteries; and due to the introduction of zinc oxide, and with the use of advantages of the tubular array structure, the technical problem of relatively poor electrochemical cycle stability of a manganese oxide negative electrode material is solved.
Description
Technical field
The present invention relates to field of material preparation, more particularly it relates to a kind of manganese oxide/zinc oxide composite hollow pipe
The preparation method of shape structure, and the manganese oxide/zinc oxide composite hollow tubular structure is used as the application of electrode material.
Background technology
With the fast development of lithium ion battery, people are to lithium ion battery high-energy-density, stable charge and discharge cycles
Performance is put forward higher requirement.As the electrode material of lithium battery, on the one hand require that it has higher lithium storage content, it is another
Aspect, due to having larger Volume Changes to cause the phenomenons such as lead rupture and further shadow during the embedded and deintercalation of lithium
Cyclical stability and the shelf life of its discharge and recharge are rung, therefore it is required that electrode material can slow down Volume Changes and thus caused
Lead rupture phenomenon.
The lithium cell cathode material based on the material with carbon element of current commercialization is compared, it is desirable to obtain the higher electricity of energy density
Pole material, research shows that many transition metal all have preferable chemical property and storage lithium performance.Wherein, manganese oxide due to
With relatively low electromotive force（1.032V）, therefore become a kind of promising lithium ion battery negative material of comparison.According to report
Road, when manganese oxide powder is used for into lithium ion battery negative material, its specific capacity can reach 650mAh/g in 0.06C, first
Discharge capacity can reach 1619mAh/g.However, after 25 circulations, its capacity will constantly be reduced to 100～400mAh/g.
In addition to Mn, Zn also shows certain storage lithium performance, typical Zn oxides zinc（ZnO）Also there is storage lithium energy
Power, can serve as more promising battery material.Keon Tae Park et al. have studied ZnO nanotube/for lithium-ion electric
The research in pond, result of study shows that ZnO nanotube/has good cyclical stability.
For the shortcoming for overcoming the polynary negative material cycle performance of lithium ion battery poor, some researchs adopt zinc oxide bag
The method covered prepares modified composite positive pole, as a result shows, the positive electrode compared with uncoated material, after coating modification
With higher efficiency first and excellent cyclical stability.Therefore, if zinc oxide is combined with manganese oxide, using the two
Thus mutually coordinated and complementation simultaneously shows more excellent chemical property and application.
Hui Xia et al. synthesize manganese oxide nano-tube array and show that it has using the method for anodic oxidation aluminium formwork
Preferable electrochemical stability and cycle performance.Gong Liangyu et al. is templated synthesis average diameter 20nm using ZnO nanorod
Left and right, the α-MnO2 nanometer rods of average length about 180nm, and show stable supercapacitor properties.But above-mentioned synthetic method
The removing step of template and the further transfer process of film are needed, and to material film structure in removing and transfer process
With the destruction of orientation, process is loaded down with trivial details, not easy to operate.
The content of the invention
The invention aims to overcome in the method for synthesis manganese oxide nanostructured of prior art, template is needed
The further transfer process of removing step and film, and the defect that industry is loaded down with trivial details, there is provided a kind of manganese oxide/zinc oxide is combined
The preparation method of hollow tubular structures.
The invention provides a kind of preparation method of manganese oxide/zinc oxide composite hollow tubular structure, the method include with
Lower step：（1）Substrate is impregnated with absolute ethyl alcohol, then this is immersed in into zinc nitrate and six methylenes with the impregnated substrate of absolute ethyl alcohol
First time hydro-thermal reaction is carried out in the solution of the ammonia of base four, to generate nanometic zinc oxide rod array film in substrate；（2）By step
（1）The substrate that the generation for obtaining has nanometic zinc oxide rod array film is immersed in manganese nitrate solution that to carry out second hydro-thermal anti-
Should.
Present invention also offers a kind of manganese oxide/zinc oxide composite hollow tubular structure prepared by above-mentioned preparation method.
The preparation method of a kind of manganese oxide/zinc oxide composite hollow tubular structure provided according to the present invention, in the preparation
In method, the present invention is template using nanometic zinc oxide rod array film, and hydro-thermal method has synthesized manganese oxide/zinc oxide composite hollow
Tubular nanostructures, without the need for the removing step of template and the further transfer process of film, process is simple, operation for the preparation method
It is convenient.In addition, using the manganese oxide/zinc oxide composite hollow tubular structure as lithium battery negative material, due between array
Free space, and the hollow-core construction of tubular structure can be prevented because volumetric expansion and contraction are made in charge and discharge process
Into lead rupture phenomenon, so as to improve electrochemical cycle stability.Further, the tube wall of nano-scale can also shorten lithium
The embedded and deintercalation process of ion.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the SEM of manganese oxide/zinc oxide composite hollow tubular structure prepared by the method according to the invention embodiment 1
Figure；
Fig. 2 is the SEM of manganese oxide/zinc oxide composite hollow tubular structure prepared by the method according to the invention embodiment 2
Figure；
Fig. 3 is the SEM of manganese oxide/zinc oxide composite hollow tubular structure prepared by the method according to the invention embodiment 3
Figure；
Fig. 4 is the manganese oxide/zinc oxide composite tubular structure prepared according to comparative example 1；
Fig. 5 is the manganese oxide/zinc oxide composite tubular structure prepared according to comparative example 2.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
A kind of preparation method of manganese oxide/zinc oxide composite hollow tubular structure provided according to the present invention, the method can
To comprise the following steps：（1）Substrate is impregnated with absolute ethyl alcohol, then this is immersed in into zinc nitrate with the impregnated substrate of absolute ethyl alcohol
With first time hydro-thermal reaction is carried out in the solution of hexamethylene tetraammonia, to generate nanometic zinc oxide rod array film in substrate；
（2）By step（1）The substrate that the generation for obtaining has nanometic zinc oxide rod array film is immersed in manganese nitrate solution and carries out second
Secondary hydro-thermal reaction.
According to the present invention, first, nanometic zinc oxide rod array film is prepared on target substrate surface.Specifically, may be used
To be soaked the substrate for cleaning up with absolute ethyl alcohol, substrate surface is set to carry basic group.Wherein, ethanol soak time is to oxygen
The density for changing zinc nano-stick array thin film plays an important role, long-time immersion can modification of surfaces make it carry-OH, and become oxygen
Change the avtive spot of zinc forming core, promote forming core and the growth of zinc oxide.According to the present invention, with absolute ethyl alcohol by the base for cleaning up
Bottom is soaked 3-4 days, preferably 2-3 days, substrate surface can be made to carry basic group.Then, then by zinc nitrate and hexa-methylene four
The solution of ammonia and the substrate that processed with the absolute ethyl alcohol constant temperature in water heating kettle carries out first time hydro-thermal reaction, to generate oxidation
Zinc nano-stick array thin film.
According in the present invention, in step（1）In, the mol ratio of the zinc nitrate and hexamethylene tetraammonia can be 1：0.8-
1.2, preferably 1：0.9-1.1, more preferably 1：1.
According to the present invention, in step（1）In, the condition of the first time hydro-thermal reaction can include：Reaction temperature is 80-
140 DEG C, preferably 90-95 DEG C, more preferably 95 DEG C；Reaction time is 1-12 hours, preferably 4-6 hours.
According to the present invention, in step（1）In, the preparation method for being provided is wide to the practicality of substrate, for example, the substrate
The one kind that can be selected from quartz glass, silicon chip, metal electrode or ceramic material.Using the preparation method of the present invention, Ke Yigeng
Different substrates are changed, therefore, it can be adapted to difference catalytic carrier and different devices.In the present invention, the substrate is preferred
For quartz glass.
According to the present invention, in step（2）In, the above-mentioned generation for preparing there is into the base of nanometic zinc oxide rod array film
Bottom is immersed in manganese nitrate solution carries out second hydro-thermal reaction.
According to the present invention, the concentration of the manganese nitrate solution can not it is too high can not be too low, the manganese nitrate solution it is dense
Degree is too high or too low, cannot all ensure that nanometic zinc oxide rod array film dissolves, therefore, in the present invention, need strict control
The concentration of the manganese nitrate solution, the concentration of the manganese nitrate solution can be 0.1-0.2M, the concentration of the manganese nitrate solution
Within the range, the nanometic zinc oxide rod array film can dissolve；Under preferable case, the concentration of the manganese nitrate solution can
Think 0.14-0.17M, more preferably 0.15M, within the range, it is more complete that the nanometic zinc oxide rod array film dissolves.
According to the present invention, in step（2）In, the condition of second hydro-thermal reaction can include：Reaction temperature is 80-
100 DEG C, preferably 90-95 DEG C, more preferably 95 DEG C；Reaction time is 60-180min, preferably 120-130min, more preferably
For 120min.
According to the present invention, on the one hand nanometic zinc oxide rod array film plays template action, on the one hand as precursor, phase
Than other template synthesis methods, inventing the preparation method for providing need not be carried out to the removing step of template and further turning for film
Journey is moved past, the method process is simple, simple operation.
According to the present invention, with the carrying out of hydro-thermal reaction, manganese oxide crystal is first before nanometic zinc oxide rod array film
Body surface carries out forming core and crystallizes, and covers into one layer of grain thin film on nanometic zinc oxide rod array film surface.Zinc oxide
The further deposition of nano-stick array thin film slow mechanism dissolved and accelerated oxidation manganese.According to solution diffusion law and geometrical principle, by
The contact probability of nanometic zinc oxide rod array film and reaction solution, manganese oxide are much larger than in the chance of tip contact reaction solution
Cover into the film of one layer of densification on nanometic zinc oxide rod array film top so that nanometic zinc oxide rod array film bottom into
For the passage of further dissolving.With the carrying out of hydro-thermal reaction, nanometic zinc oxide rod array film further dissolves, and ultimately forms
Hollow composite construction.
According to present invention also offers a kind of manganese oxide/zinc oxide composite hollow pipe prepared by preparation method described above
Shape structure.
According to the present invention, the top closure of the manganese oxide/zinc oxide composite hollow tubular structure, the manganese oxide/oxidation
The overall diameter of zinc composite hollow tubular structure is 0.5-1.5 microns, preferably 0.8-1.2 microns, more preferably 1 micron, tube wall
Wall thickness is 100-500nm, preferably 200-300nm, and length is 3-10 microns, preferably 4-5 microns.
Present invention also offers manganese oxide/zinc oxide composite hollow the tubular structure prepared by above-mentioned preparation method is used as electricity
The application of pole material.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, the pattern and size of the manganese oxide/zinc oxide composite nanostructure of preparation lead to
Cross field emission scanning electron microscope（SEM is purchased from HIT, model Hitachi S-4800）Measure；In embodiment and contrast
Chemicals used in example is purchased from lark prestige company.
Embodiment 1
Prepare nanometic zinc oxide rod array film：The quartz glass substrate for cleaning up is soaked 3 days with absolute ethyl alcohol, will
The quartz glass substrate and 0.1M zinc nitrates and each 15ml of 0.1M hexamethylene tetraammonia solution are according to volume ratio 1：1 adds 50ml
Stainless steel water heating kettle in, 95 DEG C of constant temperature are carried out after first time hydro-thermal reaction 4h, powder drying, by length have zinc oxide nano rod battle array
The quartz glass substrate of row film is rinsed well and dried.
The substrate that length has nanometic zinc oxide rod array is put in the manganese nitrate solution of 0.15M, 90 DEG C of constant temperature carry out second
After secondary hydro-thermal reaction 2h, you can obtain homodisperse and length and be about 5 microns, overall diameter is 1 micron, and pipe wall thickness is
The manganese oxide of 300nm/zinc oxide composite hollow tubular nanostructures, as shown in Figure 1.
Embodiment 2
The preparation of nanometic zinc oxide rod array film with it is identical in embodiment 1, difference be will length have zinc oxide
The quartz glass substrate of nano-stick array thin film is put in the manganese nitrate solution of 0.17M, and it is anti-that 95 DEG C of constant temperature carries out second hydro-thermal
After answering 2h, you can obtain dispersed and length and be about 5 microns, overall diameter is 1 micron, pipe wall thickness for 200nm manganese oxide/
Zinc oxide composite hollow tubular nanostructures, as shown in Figure 2.
Embodiment 3
The preparation of nanometic zinc oxide rod array film with it is identical in embodiment 1, difference be will length have zinc oxide
The quartz glass substrate of nano-stick array thin film is put in the manganese nitrate solution of 0.1M, and 95 DEG C of constant temperature carry out second hydro-thermal reaction
After 2h, you can obtain dispersed and length and be about 5 microns, overall diameter is 1.2 microns, pipe wall thickness for 500nm manganese oxide/
Zinc oxide composite hollow tubular nanostructures, as shown in Figure 3.
Comparative example 1
The preparation of nanometic zinc oxide rod array film with it is identical in embodiment 1, difference be will length have zinc oxide
The quartz glass substrate of nano-stick array thin film is put in the manganese nitrate solution of 0.05M, and it is anti-that 100 DEG C of constant temperature carries out second hydro-thermal
After answering 2h, because nano structure of zinc oxide is undissolved, the manganese oxide/zinc oxide composite tubular structure of preparation is as shown in figure 4, length
It is not hollow for 3-5 microns, a diameter of 0.5-1 microns.
Comparative example 2
The preparation of nanometic zinc oxide rod array film with it is identical in embodiment 1, difference be will length have zinc oxide
The quartz glass substrate of nano-stick array thin film is put in the manganese nitrate solution of 0.15M, and it is anti-that 140 DEG C of constant temperature carries out second hydro-thermal
After answering 2h, because nano structure of zinc oxide is undissolved, the manganese oxide/zinc oxide composite tubular structure of preparation is as shown in figure 5, length
It is not hollow for 3-5 microns, a diameter of 0.5-1 microns.
EXPERIMENTAL EXAMPLE 1
Manganese oxide/zinc oxide composite hollow tubular structure and comparative example 1 manganese oxide/oxidation prepared by embodiment 1-3
Zinc composite tubular structure carries out battery charging and discharging test as the negative material of lithium battery.
The copper plate electrode that length there are MnO2-ZnO composites is put into into vacuum drying chamber, at 80 DEG C half an hour is vacuum dried.
Dried electrode slice is immediately transferred to into the glove box full of argon atmosphere（UNLAB, German M.Braun companies）Middle dress
With battery, humidity and oxygen content are less than 1ppm.As to electrode, electrolyte is 1M LiPF6/EC to metal lithium sheet：DMC(1：1,
Vol).Complete in the glove box being assembled in of battery.Two electrode separations are opened using the barrier film of Whatman companies.By MnO2-
ZnO composites are assembled into 3020 type MnO2-ZnO/Li button cells as GND.
Charge-discharge test:The charge-discharge performance test of material is carried out in programme controlled electro-chemical test equipment
（Shenzhen Yongxing industry Neware battery test system）, be set to the form of constant current charge-discharge, the current density for adopting for setting value,
Discharge and recharge blanking voltage scope is set to 0.005V～3.0V.Charging and discharging currents are respectively adopted 50mA g-1 and 100mA g-1.
As a result show：For the manganese oxide/zinc oxide composite hollow tubular structure of embodiment of the present invention 1-3 preparation is used as lithium
The negative material of battery, from the 4th circulation until the 50th circulation maintains extraordinary cyclical stability, current density is
Its lithium storage content remains at 800mAh g-1 or so during 100mA g-1.During little multiplying power, i.e., when current density is 50mA g-1
Its lithium storage content is about 900mAh g-1.Relative to 1 manganese oxide of comparative example/zinc oxide composite tubular structure as the negative of lithium battery
Pole material, improves electrochemical cycle stability.
The manganese oxide prepared by above example 1-3/zinc oxide composite hollow tubular structure：Relative to comparative example
1-2, using the present invention preparation method prepare manganese oxide/zinc oxide composite hollow tubular structure as lithium battery negative pole material
Material, due to having bigger contact area with Li+, can accelerate the injection of Li+ and remove.Meanwhile, it is distinctive hollow based on tubulose
Structure, can have more free space to allow volume contraction of the electrode material in charge and discharge process and expansion.And using this
The preparation method of invention eliminates template removal step, and process is simple, energy consumption is low, and preparation condition is not flexibly harsh, and is adapted to big
Large-scale production.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (9)
1. a kind of preparation method of manganese oxide/zinc oxide composite hollow tubular structure, the method is comprised the following steps：
(1) substrate is impregnated with absolute ethyl alcohol, then the impregnated substrate of absolute ethyl alcohol is immersed in into zinc nitrate and hexamethylene tetraammonia
Solution in carry out first time hydro-thermal reaction, to generate nanometic zinc oxide rod array film in substrate；
(2) substrate that the generation that step (1) is obtained has nanometic zinc oxide rod array film is immersed in manganese nitrate solution is carried out
Second hydro-thermal reaction；
In step (1), the time that substrate is impregnated with absolute ethyl alcohol is 3-4 days；
In step (2), the concentration of the manganese nitrate solution is 0.1-0.2M.
2. method according to claim 1, wherein, the concentration of the manganese nitrate solution is 0.14-0.17M.
3. method according to claim 1, wherein, in step (1), the substrate is selected from quartz glass, silicon chip, metal
One kind in electrode or ceramic material.
4. method according to claim 1, wherein, in step (1), the zinc nitrate and hexamethylene tetraammonia mole
Than for 1：0.8-1.2.
5. method according to claim 4, wherein, the mol ratio of the zinc nitrate and hexamethylene tetraammonia is 1：0.9-
1.1。
6. method according to claim 1, wherein, in step (1), the condition of the first time hydro-thermal reaction includes：
Reaction temperature is 80-140 DEG C, and the reaction time is 1-12 hours.
7. method according to claim 6, wherein, the condition of the first time hydro-thermal reaction includes：Reaction temperature is 90-
95 DEG C, the reaction time is 4-6 hours.
8. method according to claim 1, wherein, in step (2), the condition of second hydro-thermal reaction includes：
Reaction temperature is 80-100 DEG C, and the reaction time is 60-180min.
9. method according to claim 8, wherein, the condition of second hydro-thermal reaction includes：Reaction temperature is 90-
95 DEG C, the reaction time is 120-130min.
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|---|---|---|---|---|
| CN102181927A (en) * | 2011-03-30 | 2011-09-14 | 北京科技大学 | Method for preparing zinc oxide nano-array on flexible substrate at low temperature |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181927A (en) * | 2011-03-30 | 2011-09-14 | 北京科技大学 | Method for preparing zinc oxide nano-array on flexible substrate at low temperature |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
Non-Patent Citations (1)
| Title |
|---|
| Tailoring CoO-ZnO nanorod and nanotube arrays for Li-ion battery anode materials;Yingjie Feng, et al.;《Journal of Materials Chemistry A》;20130528(第1期);第9655页左栏，第9656页图1-2 * |
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